CN113194605A - Liquid crystal polyester film, preparation method and application thereof, and circuit board preparation method - Google Patents
Liquid crystal polyester film, preparation method and application thereof, and circuit board preparation method Download PDFInfo
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- CN113194605A CN113194605A CN202110485298.XA CN202110485298A CN113194605A CN 113194605 A CN113194605 A CN 113194605A CN 202110485298 A CN202110485298 A CN 202110485298A CN 113194605 A CN113194605 A CN 113194605A
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- China
- Prior art keywords
- liquid crystal
- crystal polyester
- fiber
- polyester film
- polyester fiber
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 267
- 229920006267 polyester film Polymers 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 175
- 229920000728 polyester Polymers 0.000 claims abstract description 166
- 238000000034 method Methods 0.000 claims abstract description 63
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000012767 functional filler Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 39
- 239000002002 slurry Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 23
- 238000007731 hot pressing Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- -1 4-dihydroxybiphenyl Chemical compound 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011889 copper foil Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- WBPWDGRYHFQTRC-UHFFFAOYSA-N 2-ethoxycyclohexan-1-one Chemical compound CCOC1CCCCC1=O WBPWDGRYHFQTRC-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- SJPVUFMOBDBTHQ-UHFFFAOYSA-N barium(2+);dioxido(dioxo)tungsten Chemical compound [Ba+2].[O-][W]([O-])(=O)=O SJPVUFMOBDBTHQ-UHFFFAOYSA-N 0.000 claims description 2
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229940056932 lead sulfide Drugs 0.000 claims description 2
- 229910052981 lead sulfide Inorganic materials 0.000 claims description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009987 spinning Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000003490 calendering Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000090 poly(aryl ether) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 210000003781 tooth socket Anatomy 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 244000007853 Sarothamnus scoparius Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a liquid crystal polyester film, which is prepared from the following raw materials: the liquid crystal polyester fiber comprises a class A liquid crystal polyester fiber and a class B liquid crystal polyester fiber, wherein the length of the class A liquid crystal polyester fiber is less than that of the class B liquid crystal polyester fiber; the liquid crystal polyester film comprises, by weight, 1-95 parts of A-type liquid crystal polyester fibers and 5-99 parts of B-type liquid crystal polyester fibers, and the liquid crystal polyester film can also comprise functional fillers. The invention also discloses a method for preparing the liquid crystal polyester film by adopting a papermaking process technology, application and a circuit board preparation method thereof. The liquid crystal polyester film can simultaneously meet the characteristics of high tear resistance and adjustable dielectric property, has high tear resistance, excellent transverse and longitudinal tensile strength and small anisotropy, and is beneficial to the application of the liquid crystal polyester film. In addition, the production cost is greatly reduced by adopting the traditional papermaking process.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a liquid crystal polyester film, a preparation method and application thereof, and a circuit board preparation method.
Background
Thermoplastic Liquid Crystal Polymers (LCP) refer to wholly aromatic condensation polymers having relatively rigid and linear Polymer chains. When these polymers melt, they orient to form a liquid crystal phase. The liquid crystal polyester is a thermoplastic liquid crystal polymer, and the wholly aromatic polyester widely used is a liquid crystal polyester. The wholly aromatic polyester has the characteristics of high heat resistance, high chemical resistance, low water absorption, extremely high dimensional stability, excellent dielectric property and relative stability in a wide frequency range and a temperature range. The high Dk (dielectric constant) of electronic components in a circuit board can slow down the signal transmission rate, and the high Df (dielectric loss tangent angle) can partially convert the signal into heat energy to be lost in the substrate material, so that the Dk and Df need to be reduced. However, as capacitor products are miniaturized, it is desirable that the dielectric constant of the material be as high as possible for the capacitor products. Since the dielectric loss tangent angle affects the power consumption of the article, it is desirable that the dielectric loss tangent angle of the material be as low as possible.
Liquid crystalline polyesters are often prepared as films for applications in the semiconductor field. The methods for preparing liquid crystal polyester films in the prior art mainly comprise two methods: 1. adopting a casting method, a film blowing method, a calendering method and the like which are standard in the film making industry; 2. a coating method using PI (polyimide) film formation. However, the method 1 requires special processes and equipment, has high production cost and high fraction defective, and produces a film with low strength and large anisotropy, for example, CN1572468A produces a wholly aromatic polyester film by a blown film method, and produces a film with low strength and large anisotropy. The 2 nd method, which requires a liquid crystal polyester of a specific structure, generally introduces amide groups into the liquid crystal polyester to increase the polarity of the material, so that the material can be dissolved in a common solvent, and the solubility is further improved, for example, patent CN108026268A describes a method of introducing amide groups into the molecular structure of a liquid crystal polyester to increase the polarity of the material, dissolving the material in an aprotic solvent containing or not containing halogen atoms, and then evaporating the solvent to obtain a liquid crystal polyester film. However, the introduction of an amide group increases the water absorption of the liquid crystal polyester film, decreases the stability of high-frequency dielectric properties, deteriorates mechanical strength, and particularly deteriorates tear strength, and the film-forming method requires the use of a large amount of an organic solvent and is liable to cause contamination. If the halogen-containing solvent is used for the dissolution, further problems such as environment, health, and energy consumption are caused.
Different market fields have different requirements on the dielectric properties of materials. And after the second component is blended by adopting a common film preparation method, a uniform film cannot be stably prepared, so that the dielectric property of the film cannot be adjusted, and the application range of the film is further limited. Due to the limitation of the existing film forming equipment, most of the liquid crystal polyester films on the market are prepared by adopting wholly aromatic polyester with the melting point of less than 320 ℃. It is difficult to obtain stable and high-yield film products for the liquid crystal polyester with higher melting point. In the use process of the liquid crystal polyester film, the liquid crystal polyester film is often required to be cut into different shapes or drilled on the surface of the liquid crystal polyester film, so that the liquid crystal polyester film is required to have small anisotropy and high tearing strength.
In addition, the traditional film preparation method needs to be newly built with special equipment, so that the investment is huge, the technology is mastered in foreign companies at present, the domestic technology is immature, and the product yield is low.
Therefore, it is desirable to provide a novel liquid crystal polyester film and a preparation method thereof, which can be produced by adopting the existing mature equipment, reduce the equipment investment, improve the product yield and simultaneously meet the characteristics of uniform thickness, small anisotropy, high tear strength and adjustable dielectric property of the prepared liquid crystal polyester film.
Disclosure of Invention
The invention aims to at least solve the technical problems of huge equipment investment, low product yield, poor product tear strength and high product anisotropy in the prior art. For this reason, the technical researchers have conducted a great deal of research, and surprisingly found that the prepared liquid crystal polyester film forms a concrete structure similar to "steel bar" plus "cement" by using the mature spinning, paper making and calendering technologies and simultaneously using liquid crystal polyester fibers with different lengths; the liquid crystal polyester film with the structure can simultaneously meet the characteristics of high tear strength, small anisotropy, uniform thickness and adjustable dielectric property. Meanwhile, only the traditional papermaking technology is needed for preparation, so that the equipment investment is greatly reduced while the product yield is improved, and the production cost is effectively reduced.
In addition, researchers find that the liquid crystal polyester film can also be widely applied to circuit boards.
Therefore, the invention provides a liquid crystal polyester film, which comprises the following raw materials of A-type liquid crystal polyester fibers and B-type liquid crystal polyester fibers in parts by weight, wherein the A-type liquid crystal polyester fibers account for 1-95 parts by weight, and the B-type liquid crystal polyester fibers account for 5-99 parts by weight;
the fiber length L of the A-type liquid crystal polyester fiberALess than the fiber length L of the B-type liquid crystal polyester fiberB。
The fiber length L of the A-type liquid crystal polyester fiberAAnd the diameter D of the fiberAIs greater than 20; the fiber length L of the B-type liquid crystal polyester fiberBAnd the diameter D of the fiberBThe ratio of (A) is 20 or more.
Said LALess than 1mm, said LBThe range is 1-10 mm.
Said DAAnd said DBThe ranges of (A) and (B) are all 0.1-50 mu m, preferably, D isAAnd said DBThe sizes are different.
The melting point of the A-type liquid crystal polyester fiber is lower than that of the B-type liquid crystal polyester fiber, and the melting point of the A-type liquid crystal polyester fiber is at least 5 ℃ lower than that of the B-type liquid crystal polyester fiber.
The A-type liquid crystal polyester fiber and the B-type liquid crystal polyester fiber have a dielectric loss tangent angle of less than 0.005.
The liquid crystal polyester fiber of group A and the liquid crystal polyester fiber of group B both comprise a 30-100 mol% structural unit derived from at least one compound selected from p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, a 0-35 mol% structural unit derived from at least one compound selected from hydroquinone, resorcinol, 4-dihydroxybiphenyl, bisphenol A and bisphenol S, and a 0-35 mol% structural unit derived from at least one compound selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.
The thickness of the liquid crystal polyester film is less than 500 mu m; preferably, the thickness of the film is less than 200 μm; further preferably, the thickness of the liquid crystal polyester film is less than 100 μm.
The tearing strength of the liquid crystal polyester film is more than 500mN, and more preferably, the tearing strength is more than 1000 mN.
The ratio of the transverse tensile strength to the longitudinal tensile strength of the liquid crystal polyester film is 0.90-1.1, which shows that the liquid crystal polyester film has small anisotropy, and the small anisotropy of the liquid crystal polyester film indicates that the prepared liquid crystal polyester film has uniform performance, thereby being beneficial to the wide application of the liquid crystal polyester film.
Meanwhile, the invention provides a preparation method of the liquid crystal polyester film, which is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the A and B liquid crystal polyester fibers with a solvent to prepare a slurry C1;
(2) according to the papermaking process, the slurry C1 is made into paper, formed and dried to obtain liquid crystal polyester paper, and then hot-pressed to obtain the liquid crystal polyester film as claimed in any one of claims 1 to 8.
In the step (1), 0.1-5 parts of a dispersing agent is added in the process of mixing the liquid crystal polyester fiber and the solvent according to 100 parts of the solvent;
preferably, the dispersant is a silane coupling agent and/or polyethylene oxide (PEO).
In the step (1), the solvent is water or an organic solvent; the organic solvent is preferably an alcohol, for example: ethanol and propanol.
The step (1) is called defibering in which the liquid crystal polyester fibers of groups A and B are mixed with a solvent.
The liquid crystal polyester film can be prepared from the following raw materials in parts by weight:
0.2-80 parts of functional filler.
The functional filler comprises at least one of carbon fiber, glass fiber, quartz fiber, basalt fiber, PBO fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, polytetrafluoroethylene fiber, polystyrene fiber, polyether sulfone fiber, polyether ketone fiber, polyphenylene sulfide fiber or aramid fiber.
The functional filler further comprises a dielectric powder material;
the particle size of the dielectric powder material is less than 20 μm; preferably, the particle size of the dielectric powder material is less than 10 μm.
The dielectric powder material is a high dielectric powder material with a dielectric constant larger than 5 or a low dielectric powder material with a dielectric constant smaller than 5.
The high dielectric powder material is at least one selected from barium titanate, calcium titanate, strontium titanate, barium zirconate, barium tungstate, lithium iodate, lithium aluminate, lead sulfide, lead hafnate or lead titanate.
The low dielectric powder material is selected from at least one of inorganic low dielectric constant material, organic low dielectric constant material, porous low dielectric constant material or composite low dielectric constant material.
Preferably, the inorganic low-dielectric constant material is selected from at least one of fluorinated silica glass, hollow glass beads, silicon nitride or silicon oxide.
Preferably, the organic low dielectric constant material is selected from at least one of polyvinyl aryl compound, polyimide, polyaryl hydrocarbon, polyaryl ether, parylene, polypropylene, polyethylene, fluorine-doped polyimide, amorphous polytetrafluoroethylene, fluorine-doped polyarylether, methyl silsesquioxane, bis-ethoxysilane, norbornene, hydrogen silsesquioxane, fluorine-doped benzoxazole polymer or fluorine-doped benzoxazine polymer.
Preferably, the porous low dielectric constant material is selected from at least one of porous silsesquioxane, porous polyimide, porous polyethylene, porous polytetrafluoroethylene, porous polysiloxane, porous alumina, or porous forsterite.
Preferably, the composite low dielectric constant material is at least one selected from a zeolite-polyimide composite porous material, a BN/SICO composite porous material (http:// www.docin.com/p-960999976.html page 12 describes a BN/SICO composite porous material), a polystyrene-silica composite material, and a polyimide-silica composite material.
Meanwhile, the invention provides a preparation method of the liquid crystal polyester film containing the functional fiber filler, which comprises the following steps:
(1) performing the defibering process to obtain slurry C1;
(2) mixing and dispersing the functional filler and the solvent to prepare slurry D1, and then mixing slurry C1 and slurry D1 to prepare slurry S;
(3) and (3) according to a papermaking process, making and forming the slurry S, drying to obtain liquid crystal polyester paper, and then hot-pressing to obtain the liquid crystal polyester film containing the functional fiber filler.
In the two preparation methods, before the liquid crystal polyester fiber is mixed with the solvent, the liquid crystal polyester fiber needs to be washed: washing with a detergent at 10-80 ℃ for 10-120 minutes; wherein, the detergent is preferably sodium dodecyl benzene sulfonate solution.
Some oil agents are added in the spinning process of the liquid crystal polyester fiber, and most of the oil agents are hydrophobic substances, so that the hydrophobicity of the liquid crystal polyester fiber is further increased. And because of the existence of the oil agent, small bubbles are easily adsorbed on the surface of the liquid crystal polyester fiber in the stirring process of the slurry, the dispersion of the liquid crystal polyester fiber is not facilitated, and the liquid crystal polyester fiber is easily flocculated. Therefore, the liquid crystal polyester fibers are washed with the detergent, which contributes to the dispersion of the liquid crystal polyester fibers.
The mass ratio of the liquid crystal polyester fiber to the solvent is (0.003-0.5): 100, respectively; preferably, the mass ratio of the liquid crystal polyester fiber to the solvent is (0.003-0.1): 100.
the mass ratio of the functional filler to the liquid crystal polyester fiber is (1-200): 100, respectively; preferably, the mass ratio of the functional filler to the liquid crystal polyester fiber is (10-100): 100.
the papermaking process is a conventional papermaking process, and the concentration of the pulp on the net has great influence on papermaking performance in the papermaking and forming process of the pulp. The concentration of the upper mesh pulp is more than 0.5:100, so that the crowding factor of the liquid crystal polyester fiber in a solvent such as water is increased rapidly, the phenomena that the collision times between the liquid crystal polyester fibers are increased, the dispersion condition is worsened rapidly, the flocculation degree is increased, and the forming difficulty of the liquid crystal polyester paper is further increased. Therefore, the concentration of the liquid crystal polyester fiber and the functional filler is selected in the preparation process, and the liquid crystal polyester paper is favorably formed.
The hot-pressing temperature is higher than the initial flowing temperature of the B-type liquid crystal polyester fiber and lower than the melting point of the B-type liquid crystal polyester fiber plus 30 ℃; for example, when the initial flow temperature of the liquid crystal polyester is 275 ℃, the melting point is 300 ℃; the temperature of the hot pressing is more than 275 deg.c and less than 330 deg.c.
Preferably, the hot-pressing temperature is higher than the initial flowing temperature of the B-type liquid crystal polyester and at least lower than the melting point of the B-type liquid crystal polyester plus 15 ℃; preferably, the temperature of the hot pressing process is 250-400 ℃.
The liquid crystal polyester fibers with different lengths are adopted, and in the pressing process, the hot pressing temperature is controlled to be lower than the melting point of the long fibers by controlling the hot pressing temperature and time, so that the liquid crystal polyester fibers with smaller sizes are melted, the liquid crystal polyester fibers with larger sizes are not melted, and a concrete structure similar to a steel bar (corresponding to the liquid crystal polyester fibers with larger sizes) and cement (corresponding to the liquid crystal polyester fibers with smaller sizes) is formed, and therefore, the high tear strength is achieved. And since the microscopic arrangement of the liquid crystal polyester fiber having a large size is random in the paper making process, the number of the liquid crystal polyester fiber in each direction is the same in a macroscopic view, and thus the anisotropy of the liquid crystal polyester film is small.
The hot pressing is rolling or surface pressing, and inert gas is adopted for protection in the hot pressing process.
The process of preparing the slurry needs to use a disc grinder, the grinding paddle of the disc grinder mainly depends on the high-speed rotation of a movable disc to generate huge centrifugal force, and because the acting force continuously throws pulp fibers which are violently and turbulently moved in a tooth socket to a tooth grinding surface, the pulp fibers have the tendency of radial movement and the tendency of circular movement, and the pulp fibers frequently fall between the tooth pattern and the tooth socket. During this movement, the pulp is subjected to centrifugal, torsional, shear, pultrusion and hydraulic impacts, with consequent variations in defibration, transverse cutting, longitudinal splitting and fibrillation of the pulp fibres. The disk grinding equipment commonly used in papermaking is divided into two types, one is mainly used for cutting and the other is mainly used for devillicating the silk brooms.
After the liquid crystal polyester film is prepared in the preparation process, the method further comprises the following film heat treatment steps: placing the liquid crystal polyester film in a vacuum state or under the protection of inert gas, and preserving heat for 0.1-36 hours at 200-400 ℃; preferably, the temperature is kept at 220-320 ℃ for 2-24 hours.
And a certain traction force is required to be kept in the transverse direction and the longitudinal direction of the liquid crystal polyester film in the heat treatment process.
In addition, the invention also provides a circuit board substrate which comprises metal foil and the liquid crystal polyester film; preferably, the metal foil is at least one of copper foil, aluminum foil, gold foil, nickel foil or silver foil; more preferably, the copper foil is a rolled copper foil or an electrolytic copper foil.
The thickness of the metal foil is 9-70 mu m.
The circuit board substrate structure is a laminated structure with two or more layers; wherein the liquid crystal polyester film layer is adjacent to the metal foil layer.
The circuit board substrate structure is characterized in that the structure between the liquid crystal polyester film layer and the metal foil layer is as follows: the liquid crystal polyester film layer and the metal foil layer are of a two-layer structure, or a three-layer structure formed by laminating the metal foil on two sides of the liquid crystal polyester film layer, or a five-layer structure formed by alternately laminating the liquid crystal polyester film layer and the metal foil layer.
The thickness range of the circuit board substrate is 10-500 mu m, and the peel strength is greater than 0.5N/mm; preferably, the peel strength is greater than 1N/mm.
Meanwhile, the invention also provides a preparation method of the circuit board substrate, which comprises the following steps: and pressing the metal foil and the liquid crystal polyester film at the temperature of 250-400 ℃ to obtain the circuit board substrate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a tear-resistant liquid crystal polyester film and a preparation method thereof, which adopt mature spinning, papermaking and calendering technologies, solve the technical problems that the traditional film preparation method needs to newly build special equipment, the investment is huge, the domestic technology is not mature, and the product yield is low, effectively reduce the equipment investment and improve the product yield.
(2) Liquid crystal polyester fibers with different lengths are adopted to prepare the tear-resistant liquid crystal polyester film according to a proper dosage proportion, and the liquid crystal polyester fibers with smaller sizes are melted while the liquid crystal polyester fibers with larger sizes are not melted by controlling the hot pressing temperature and time in the pressing process, so that a concrete structure similar to 'reinforcing steel bar' + 'cement' is formed, and the strength of the material is higher than that of a material which is only 'cement'; in addition, in the papermaking process, the microscopic arrangement of the liquid crystal polyester fibers with larger sizes is random, so that the quantity of the liquid crystal polyester fibers in all directions is the same in macroscopic view, the anisotropy is small, and the tear strength of the prepared liquid crystal polyester film is high.
(3) The tear strength of the liquid crystal polyester film prepared by the invention is more than 500N/m, the ratio of the transverse tensile strength to the longitudinal tensile strength is 0.9-1.1, the anisotropy of the liquid crystal polyester film is small, and the application of the liquid crystal polyester film is facilitated.
(4) The functional filler is added in the preparation process of the liquid crystal polyester film, so that the dielectric property, such as the dielectric constant, of the prepared liquid crystal polyester film is adjustable, and the application of the liquid crystal polyester film is expanded.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The method for testing the ratio of the transverse tensile strength to the longitudinal tensile strength of the liquid crystal polyester film comprises the following steps:
the liquid crystal polyester film obtained was divided into 10 equal parts in the transverse/longitudinal direction, 10 test pieces of 1cm in width and 15cm in length were cut, each test piece was stretched at a speed of 10mm/min at room temperature at a clamp pitch of 10cm using a universal tester (provided by seikagaku corporation, acquired from north Hebei province), the tensile strength was measured according to ISO527, the tensile strength was determined as the ratio of the transverse tensile strength to the longitudinal tensile strength by dividing the transverse tensile strength by the longitudinal tensile strength.
The method for testing the thickness of the liquid crystal polyester film comprises the following steps:
the thickness of the obtained film was measured at an lcm interval in the transverse direction using a digital thickness meter (model GY-120, available from Guangyi instruments Co., Ltd., Dongguan), and 10 data were taken. The arithmetic mean of the measured values obtained was taken as the thickness of the liquid-crystalline polyester film,
is the arithmetic mean and σ is the worst.
Dk. The test conditions for Df were: the frequency was measured at 10GHz using the apparatus Agilent N5230A, clamp SPDR.
The test conditions for peel strength were: the peel strength of the metal layer at 90 ℃ was tested by IPC-TM-6502.4.9. The data is recorded as the lower peel strength of the two sides of the double panel.
Tear test standard IEC 60819-2: 2001, unit mN.
Initial flow temperature: a temperature at which the melt index is between 0.1 and 0.2g/10min under a weight of 20 kg.
Production example 1: preparation of liquid crystalline polyester fiber
The preparation of the liquid crystal polyester fiber comprises the following steps:
in a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 1027.5g of 4-hydroxybenzoic acid (HBA), 470g of 6-hydroxy-2-naphthoic acid (HNA), 1122g of acetic anhydride, 200.0g of acetic acid were charged, the reactor was purged by evacuation and dry nitrogen flushing, 0.3g of 1-methylimidazole was added, stirring was carried out at a speed of 150 rpm under nitrogen protection, the temperature was raised to 150 ℃ over 60 minutes, and refluxing was carried out at that temperature for 60 minutes, 13.0g of phenol was charged into the reactor, the temperature was raised to 340 ℃ over 120 minutes, during which by-product acetic acid was removed by distillation, after 30 minutes of constant temperature at 340 ℃, the pressure was gradually lowered to about 100Pa to maintain vacuum over 20 minutes until the torque increased by more than 30%, after the reaction was completed, the prepolymer was taken out, the obtained prepolymer was cooled to room temperature and then pulverized by a pulverizer, and the pulverized prepolymer was subjected to solid-phase polymerization by: heating from room temperature to 230 ℃ within 3 hours under the negative pressure of 200Pa, then heating from 230 ℃ to 265 ℃ within 3 hours, and keeping at 265 ℃ for 10 hours; liquid-crystalline polyester P1 was obtained.
The liquid crystalline polyester P1 was tested to have a melting point of 300 deg.C, an initial flow temperature of 285 deg.C, a Dk of 2.9, and a Df of 0.0012.
Drying liquid crystal polyester P1 in a 150 ℃ vacuum dryer for 12 hours, after the moisture content is less than 10ppm, using a twin screw extruder melt extrusion, using a gear pump metering, liquid crystal polyester P1 supplied to the spinning pack, from the extruder outlet to the spinning pack spinning temperature of 330 ℃, filter mesh number is 300, using 58 hole diameter 0.15mm spinneret with the discharge rate of 18 cc/min liquid crystal polyester P1, 58 filaments at the same time with 900 m/min wound around the aluminum alloy reel (thermal expansion coefficient of 2.5 x 10)-5) Then, the fiber was heated from room temperature to 240 ℃ for 5 hours under a negative pressure of 100Pa, further heated from 240 ℃ to 270 ℃ for 2 hours, and kept at 270 ℃ for 18 hours to conduct heat treatment, and after the heat treatment, the fiber was rewound from a heat-treated bobbin to a paper tube at 265 ℃ at a draw ratio of 400 m/min of 1:1.2 (draw ratio between transverse direction and longitudinal direction) to obtain a liquid crystal polyester fiber X1.
The liquid crystal polyester fiber X1 was tested to have a diameter of 9 μm.
Production example 2: preparation of liquid crystalline polyester fiber
The preparation of the liquid crystal polyester fiber comprises the following steps:
in a reactor equipped with a stainless steel type C stirrer, a torque meter, a nitrogen introduction tube, a thermometer, a pressure gauge and a reflux condenser, 994.5g of p-hydroxybenzoic acid, 299.0g of terephthalic acid, 99.7g of isophthalic acid, 446.9g of 4, 4' -dihydroxybiphenyl, 1347.6g of acetic anhydride, 200.0g of acetic acid were charged, the reactor was purged by evacuation and dry nitrogen flushing, 0.18g of 1-methylimidazole was added, stirring was carried out at a rate of 75 rpm under nitrogen protection, the temperature was raised to 150 ℃ over 60 minutes and refluxed at this temperature for 60 minutes, after 13.0g of benzylamine and 1.84g of calcium acetate were charged into the reactor, the temperature was raised to 340 ℃ over 20 minutes, during which the by-produced acetic acid was removed by distillation, after 30 minutes of incubation at 340 ℃, the pressure was gradually lowered to about 100Pa over 20 minutes and kept under vacuum, until the torque increased by more than 30%, the reaction was terminated, the prepolymer was taken out, the obtained prepolymer was cooled to room temperature and then pulverized by a coarse pulverizer, and the pulverized prepolymer was subjected to solid phase polymerization by: the liquid-crystalline polyester P2 was obtained by heating from room temperature to 250 ℃ over 3 hours in a nitrogen atmosphere, then from 250 ℃ to 295 ℃ over 5 hours and holding at 295 ℃ for 2.5 hours.
The liquid-crystalline polyester P2 was tested to have a melting point of 335 deg.C, an initial flow temperature of 320 deg.C, a Dk of 3.1 and a Df of 0.0012.
Drying liquid crystal polyester P2 in a 150 ℃ vacuum dryer for 12 hours, after the moisture content is less than 10ppm, using a twin screw extruder melt extrusion, using a gear pump metering, liquid crystal polyester P2 supplied to the spinning pack, from the extruder outlet to the spinning pack spinning temperature of 360 ℃, filter mesh number is 300, using 58 hole diameter 0.2mm spinneret with the discharge rate of 18 cc/min liquid crystal polyester P2, 58 filaments at the same time with 600 m/min wound around the aluminum alloy reel (thermal expansion coefficient of 2.5 x 10)-5) Then, the fiber was heated from room temperature to 280 ℃ for 6 hours at a negative pressure of 100Pa, further heated from 280 ℃ to 310 ℃ for 4 hours, and kept at 310 ℃ for 10 hours to conduct heat treatment, and after the heat treatment, the fiber was rewound from a heat-treated bobbin to a paper tube at 285 ℃ at a draw ratio of 400 m/min of 1:1.1 (draw ratio between transverse direction and longitudinal direction) to obtain a liquid crystal polyester fiber X2.
The liquid crystal polyester fiber X2 was tested to have a diameter of 10 μm.
Example 1: preparation of liquid-crystalline polyester film
The liquid crystal polyester film comprises the following components in parts by weight:
class A liquid crystal polyester fiber X1 (L)A<1mm，DA9 μm) of 30 parts of (c),
b-type liquid crystal polyester fiber X1 (L)B＝1～10mm，DB9 μm) 70 parts;
the group a liquid crystal polyester fiber X1 and the group B liquid crystal polyester fiber X1 were obtained by shearing the liquid crystal polyester fiber X1 obtained in production example 1.
A preparation method of a tear-resistant liquid crystal polyester film comprises the following steps:
(1) mixing the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X1 with water (the mass ratio of the total mass of the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X1 to the water is 0.1:100) to prepare a slurry C1;
(2) according to the papermaking process, the slurry C1 was formed into a sheet, dried to obtain a liquid crystal polyester paper, and then hot-pressed to obtain a liquid crystal polyester film F1.
The papermaking process in the step (2) is the prior art; the hot pressing in the step (2) is carried out at the temperature of 310 ℃ and under the pressure of 50MPa for 30 seconds.
The liquid-crystalline polyester film F1 was tested to have a tear resistance of 1500mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 0.98, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 2.8 and Df of 0.0010.
Example 2: preparation of liquid-crystalline polyester film
The liquid crystal polyester film comprises the following components in parts by weight:
class A liquid crystal polyester fiber X1 (L)A<1mm, DA 9 μm) 70 parts
B-type liquid crystal polyester fiber X2 (L)B＝1～10mm，DB10 μm) 30 parts;
the group a liquid crystal polyester fiber X1 and the group B liquid crystal polyester fiber X2 were obtained by cutting the liquid crystal polyester fiber X1 obtained in production example 1 and the liquid crystal polyester fiber X2 obtained in production example 2.
A preparation method of a tear-resistant liquid crystal polyester film comprises the following steps:
(1) mixing the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X2 with water (the mass ratio of the total mass of the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X2 to the water is 0.01:100) to prepare a slurry C1;
(2) according to the papermaking process, the slurry C1 was formed into a sheet, dried to obtain a liquid crystal polyester paper, and then hot-pressed to obtain a liquid crystal polyester film F2.
The papermaking process in the step (2) is the prior art; the hot pressing in the step (2) is carried out at the temperature of 310 ℃ and under the pressure of 100MPa for 30 seconds.
The liquid-crystalline polyester film F2 was tested to have a tear resistance of 1600mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 0.97, a thickness of 50 μm, a relative deviation of film thickness of 3%, Dk of 2.9 and Df of 0.0009.
Example 3: preparation of liquid-crystalline polyester film
Example 3 is different from example 1 only in that the liquid crystal polyester fiber X1 is treated as follows before the liquid crystal polyester fiber X1 is mixed with the solvent in step (1): with a concentration of 1X 10-3A liquid-crystalline polyester film F3 was obtained in the same manner as in example 1 except that the washing was carried out at 20 ℃ for 60 minutes in mol/L of a solution of dialkyl sodium benzenesulfonate as a detergent.
The liquid-crystalline polyester film F3 was tested to have a tear resistance of 1800mN, a ratio of transverse tensile strength to longitudinal tensile strength of 0.98, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 2.8 and Df of 0.0010.
Example 4: preparation of liquid-crystalline polyester film
Example 4 was different from example 3 only in that 0.1 part by weight of a dispersant PEO was added in step (1) and the other preparation process was the same as example 3, to obtain a liquid-crystalline polyester film F4.
The liquid crystal polyester film F4 was tested to have a tearability of 1850mN, a ratio of the transverse direction tensile strength to the longitudinal direction tensile strength of 1.01, a thickness of 75 μm, a relative deviation of the film thickness of 3%, Dk of 2.8 and Df of 0.0010.
Example 5: preparation of liquid-crystalline polyester film
The liquid crystal polyester film comprises the following components in parts by weight:
class A liquid crystal polyester fiber X1 (L)A<1mm，DA9 μm) 30 parts
B-type liquid crystal polyester fiber X2 (L)B＝1～10mm，DB10 μm) 65 parts
5 parts of polystyrene fiber;
the group a liquid crystal polyester fiber X1 and the group B liquid crystal polyester fiber X2 were obtained by cutting the liquid crystal polyester fiber X1 obtained in production example 1 and the liquid crystal polyester fiber X2 obtained in production example 2.
A preparation method of a tear-resistant liquid crystal polyester film comprises the following steps:
(1) mixing the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X2 with water (the mass ratio of the total mass of the A-type liquid crystal polyester fiber X1 and the B-type liquid crystal polyester fiber X2 to the water is 0.03:100) to prepare a slurry C1;
(2) mixing and dispersing polystyrene fibers and water (the mass ratio of the polystyrene fibers to the water is 0.1:100) to prepare a slurry D1, and then mixing the slurry C1 and the slurry D1 to prepare a slurry S;
(3) according to the papermaking process, the slurry S is formed into a shape by papermaking and dried to obtain a liquid crystal polyester paper, and then hot-pressed to obtain a liquid crystal polyester film F5.
The papermaking process in the step (3) is the prior art; and (4) pressing for 50 seconds at the hot pressing temperature of 300 ℃ and the pressure of 100MPa in the step (3).
The liquid-crystalline polyester film F5 was tested to have a tear resistance of 1700mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 0.98, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 2.7 and Df of 0.0010.
Example 6: preparation of liquid-crystalline polyester film
Example 6 is different from example 5 in that in the step (2), 30 parts of hollow glass microspheres (having a particle size of 0.5 to 1 μm) were used in place of the polystyrene fibers in example 5, and the other preparation method was the same as example 5, to obtain a liquid-crystalline polyester film F6.
The liquid-crystalline polyester film F6 was tested to have a tear resistance of 1000mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 1.02, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 2.4 and Df of 0.0010.
Example 7: preparation of liquid-crystalline polyester film
In comparison with example 5, example 7 was different in that in the step (2), 10 parts of barium titanate (particle diameter of 0.1 to 1 μm) was used in place of the polystyrene fiber in example 5, and the same preparation method as in example 5 was used to obtain a liquid-crystalline polyester film F7.
The liquid-crystalline polyester film F7 was tested to have a tear resistance of 1200mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 0.98, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 7.6 and Df of 0.0010.
Example 8: preparation of liquid-crystalline polyester film
In comparison with example 5, example 8 is different in that, after the liquid crystal polyester film is obtained in step (3), the liquid crystal polyester film is placed in a vacuum state or under an inert gas atmosphere, and heat-preserved at 265 ℃ for 5 hours, followed by hot pressing to obtain a liquid crystal polyester film F8.
The liquid-crystalline polyester film F8 was tested to have a tear resistance of 2000mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 0.98, a thickness of 75 μm, a relative deviation of film thickness of 3%, Dk of 2.8 and Df of 0.0010.
Example 9: preparation of liquid-crystalline polyester film
Compared with example 5, example 9 is different in that after the liquid crystal polyester film is obtained in step (3), the liquid crystal polyester film is kept at 290 ℃ for 4 hours in a vacuum state or under the protection of inert gas, and a liquid crystal polyester film F9 is obtained.
The liquid crystal polyester film F9 was tested to have a tearability of 2300mN, a ratio of the transverse tensile strength to the longitudinal tensile strength of 0.98, a thickness of 50 μm, a relative deviation of the film thickness of 3%, a Dk of 2.7 and a Df of 0.0010.
Example 10: preparation of liquid-crystalline polyester film
Compared with example 9, example 10 is different in that the liquid crystal polyester fiber is subjected to the following treatment before being mixed with the solvent in step (1): with a concentration of 1X 10-3Washing the dialkyl sodium benzenesulfonate solution at 20 deg.c for 60 min; a liquid-crystalline polyester film F10 was obtained.
The liquid crystal polyester film F10 was tested to have a tear resistance of 2500mN, a ratio of transverse direction tensile strength to longitudinal direction tensile strength of 1.03, a thickness of 50 μm, a relative deviation of film thickness of 3%, Dk of 2.7 and Df of 0.0010.
Comparative example 1: method for preparing liquid crystal polyester film by film blowing method
The liquid crystal polyester P1 obtained in production example 1 was heated and melted by using a single-screw extruder with a cylinder temperature set at 300 ℃ and the melt obtained was extruded through a circular die with a diameter of 40mm and a gap interval of 0.5mm at a die temperature of 325 ℃ and a shear rate of 900 seconds-1The resulting film was extruded upward, expanded at a blow ratio of 4.7 and a stretch ratio of 2.1, cooled, and then drawn by nip rolls to obtain a liquid crystal polyester film having a thickness of 50 μm.
The liquid crystal polyester film was tested to have a tearability of 400mN, a relative deviation of the thickness of the liquid crystal polyester film of 21%, a ratio of the transverse direction tensile strength to the longitudinal direction tensile strength of 0.78, Dk of 2.9 and Df of 0.0013.
Comparative example 2: coating method for preparing liquid crystal polyester film
8g of the liquid crystal polyester P2 powder obtained in production example 2 and 0.08g of phenyl acetate were added to 92g of P-chlorophenol, heated to 120 ℃ to give a mixed solution, the mixed solution was coated on the surface of a copper foil, evaporated at 100 ℃ for 1 hour to remove the P-chlorophenol, and then, heat-treated by a hot air flow drier under a nitrogen atmosphere at a temperature of 280 ℃ for 60 minutes to obtain a liquid crystal polyester film having a copper foil, and the liquid crystal polyester film having a copper foil was immersed in an iron chloride solution to remove the copper foil to obtain a liquid crystal polyester film.
The tested liquid crystal polyester film had a tearability of 300mN and a thickness of 50 μm, a ratio of tensile strength in the transverse direction to tensile strength in the longitudinal direction of 0.94, and a relative deviation of the film thickness of 7%. Dk is 3.2 and Df is 0.0013.
Comparative example 3: coating method for preparing liquid crystal polyester film
8g of the liquid crystal polyester P2 powder obtained in production example 2 and water (the mass ratio of the liquid crystal polyester P2 to the water is 0.03:100) were mixed to obtain slurry C1'; mixing and dispersing polystyrene fibers and water (the mass ratio of the polystyrene fibers to the water is 0.1:100) to prepare a slurry D1', and then mixing the slurry C1' and the slurry D1 'to prepare a slurry S'; according to the papermaking process, the slurry S' is made into paper, formed and dried to obtain liquid crystal polyester paper, and then hot-pressed to obtain the liquid crystal polyester film. Wherein the hot pressing temperature is 300 deg.C, and the pressure is 100MPa for 50 s.
The tested liquid crystal polyester film had a tearability of 600mN and a thickness of 50 μm, a ratio of the tensile strength in the transverse direction to the tensile strength in the longitudinal direction of 0.97, and a relative deviation of the film thickness of 7%. Dk is 3.2 and Df is 0.0014.
The performance indexes of the above examples and comparative examples are shown in the following table 1:
TABLE 1 table of performance indexes of examples and comparative examples
Application example 1: preparation of FPC substrate
The copper foil and the liquid crystal polyester film F1 obtained in example 1 were pressed at a temperature of 325 ℃ and a pressure of 40MPa for 60 seconds to obtain an FPC substrate having a thickness of 100. mu.m.
The peel strength of the FPC substrate was tested to be 1.0N/mm.
Application example 2: preparation of FPC substrate
The copper foil and the liquid crystal polyester film obtained in example 9 were pressed at a temperature of 300 ℃ and a pressure of 45MPa for 180 seconds to obtain an FPC substrate having a thickness of 100. mu.m.
The peel strength of the FPC substrate was tested to be 1.3N/mm.
As can be seen from the comparison between the above examples and comparative examples, the tear-resistant liquid crystal polyester film prepared by adopting liquid crystal polyester fibers with different lengths and by mature spinning, papermaking and calendering technologies has the advantages that the anisotropy is obviously reduced and the tear strength is obviously improved compared with the liquid crystal polyester film prepared by the traditional coating method and the traditional film blowing method; on the other hand, the invention adopts mature spinning, papermaking and calendaring technologies, solves the technical problems that the traditional film-making method needs to newly build special equipment, the investment is huge, the domestic technology is not mature, and the product yield is low, effectively reduces the equipment investment, and improves the product yield.
Although the present invention has been described in detail with reference to the above embodiments, the above description is only for the purpose of facilitating the understanding of the present invention by the skilled in the art, and is not intended to limit the scope of the present invention, so that the equivalent changes and modifications in the shape, structure, and spirit of the present invention described in the claims are included in the scope of the present invention.
Claims (31)
1. The liquid crystal polyester film comprises the following preparation raw materials in parts by weight: the liquid crystal polyester fiber comprises a type A liquid crystal polyester fiber and a type B liquid crystal polyester fiber, wherein the weight part of the type A liquid crystal polyester fiber is 1-95, and the weight part of the type B liquid crystal polyester fiber is 5-99;
the method is characterized in that: the fiber length L of the A-type liquid crystal polyester fiberALess than the fiber length L of the B-type liquid crystal polyester fiberB。
2. The liquid-crystalline polyester film according to claim 1, wherein: the fiber length L of the A-type liquid crystal polyester fiberAAnd the diameter D of the fiberAThe ratio of (A) to (B) is more than 20, and the fiber length L of the B-type liquid crystal polyester fiberBAnd the diameter D of the fiberBThe ratio of (A) is 20 or more.
3. The liquid-crystalline polyester film according to claim 1, wherein: said LALess than 1mm, said LBThe range is 1-10 mm.
4. According to any one of claim 1The liquid crystal polyester film is characterized in that: diameter D of the A-type liquid crystal polyester fiberAAnd the diameter D of the B-type liquid crystal polyester fiberBThe range of (A) is 0.1-50 μm; preferably, said diameter DAAnd DBDifferent.
5. The liquid-crystalline polyester film according to claim 1, wherein: the melting point of the A-type liquid crystal polyester fiber is lower than that of the B-type liquid crystal polyester fiber.
6. The liquid-crystalline polyester film according to claim 5, wherein: the melting point of the A-type liquid crystal polyester fiber is at least 5 ℃ lower than that of the B-type liquid crystal polyester fiber.
7. The liquid-crystalline polyester film according to claim 1, wherein: the A-type liquid crystal polyester fiber and the B-type liquid crystal polyester fiber have a dielectric loss tangent angle of less than 0.005.
8. The liquid-crystalline polyester film according to claim 1, wherein: the liquid crystal polyester fiber of group A and the liquid crystal polyester fiber of group B both comprise a 30-100 mol% structural unit derived from at least one compound selected from p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, a 0-35 mol% structural unit derived from at least one compound selected from hydroquinone, resorcinol, 4-dihydroxybiphenyl, bisphenol A and bisphenol S, and a 0-35 mol% structural unit derived from at least one compound selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.
9. The liquid-crystalline polyester film according to claim 1 to 8, wherein: the thickness of the liquid crystal polyester film is less than 500 mu m; preferably, the thickness of the film is less than 200 μm; further preferably, the thickness of the liquid crystal polyester film is less than 100 μm.
10. The liquid-crystalline polyester film according to claim 1 to 8, wherein: the ratio of the transverse tensile strength to the longitudinal tensile strength of the liquid crystal polyester film is 0.90-1.1.
11. The liquid-crystalline polyester film according to any one of claims 1 to 10, wherein: the preparation raw materials also comprise the following components in parts by weight:
0.2-80 parts of functional filler.
12. The liquid-crystalline polyester film according to claim 11, wherein: the functional filler comprises at least one of carbon fiber, glass fiber, quartz fiber, basalt fiber, PBO fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, polytetrafluoroethylene fiber, polystyrene fiber, polyether sulfone fiber, polyether ketone fiber, polyphenylene sulfide fiber or aramid fiber.
13. The liquid-crystalline polyester film according to claim 11, wherein: the functional filler further comprises a dielectric powder material, and the particle size of the dielectric powder material is less than 20 μm; preferably, the particle size of the dielectric powder material is less than 10 μm.
14. The liquid-crystalline polyester film according to claim 13, wherein: the dielectric powder material is a high dielectric powder material with a dielectric constant larger than 5 or a low dielectric powder material with a dielectric constant smaller than 5.
15. The liquid-crystalline polyester film according to claim 14, wherein: the high dielectric powder material is at least one selected from barium titanate, calcium titanate, strontium titanate, barium zirconate, barium tungstate, lithium iodate, lithium aluminate, lead sulfide, lead hafnate or lead titanate.
16. The liquid-crystalline polyester film according to claim 14, wherein: the low dielectric powder material is selected from at least one of inorganic low dielectric constant material, organic low dielectric constant material, porous low dielectric constant material or composite low dielectric constant material.
17. A method for producing a liquid-crystalline polyester film according to any one of claims 1 to 10, characterized by comprising: the method comprises the following steps:
(1) mixing the A and B liquid crystal polyester fibers with a solvent to prepare a slurry C1;
(2) the liquid crystal polyester film according to any one of claims 1 to 10 is obtained by forming the slurry C1 into a paper according to a papermaking process, drying the paper to obtain a liquid crystal polyester paper, and hot-pressing the paper.
18. The method of claim 17, wherein: in the step (1), 0.1-5 parts of a dispersing agent is added in the process of mixing the liquid crystal polyester fiber and the solvent according to 100 parts of the solvent;
preferably, the dispersant is a silane coupling agent and/or polyethylene oxide (PEO).
19. A method for producing a liquid-crystalline polyester film according to any one of claims 11 to 16, characterized by: the method comprises the following steps:
(1) mixing the A and B liquid crystal polyester fibers with a solvent to prepare a slurry C1;
(2) mixing and dispersing the functional filler and a solvent to prepare slurry D1, and then mixing slurry C1 and slurry D1 to prepare slurry S;
(3) the liquid crystal polyester film according to any one of claims 11 to 16 is obtained by forming the slurry S into a sheet, drying the sheet to obtain a liquid crystal polyester paper, and then hot-pressing the liquid crystal polyester paper.
20. The method according to any one of claims 17 to 19, wherein: before the liquid crystal polyester fiber and the solvent are mixed, washing the liquid crystal polyester fiber: washing with a detergent at 10-80 ℃ for 10-120 minutes;
wherein, the detergent is preferably sodium dodecyl benzene sulfonate solution.
21. The method according to any one of claims 17 to 19, wherein: the mass ratio of the liquid crystal polyester fiber to the solvent is (0.003-0.5): 100, respectively;
preferably, the mass ratio of the liquid crystal polyester fiber to the solvent is (0.003-0.1): 100.
22. the method according to any one of claims 17 to 19, wherein: the hot-pressing temperature is higher than the initial flowing temperature of the B-type liquid crystal polyester fiber and lower than the melting point of the B-type liquid crystal polyester fiber plus 30 ℃;
preferably, the hot-pressing temperature is higher than the initial flowing temperature of the B-type liquid crystal polyester and at least lower than the melting point of the B-type liquid crystal polyester plus 15 ℃;
preferably, the temperature of the hot pressing process is 250-400 ℃.
23. The method according to any one of claims 17 to 19, wherein: the hot pressing is rolling or surface pressing, and inert gas is adopted for protection in the hot pressing process.
24. The method according to any one of claims 17 to 23, wherein: after the liquid crystal polyester film is prepared, the method also comprises the following heat treatment steps: placing the liquid crystal polyester film in a vacuum state or under the protection of inert gas, and preserving heat for 0.1-36 hours at 200-400 ℃; preferably, the temperature is kept at 220-320 ℃ for 2-24 hours.
25. The method of claim 24, wherein: and a certain traction force is kept in the transverse direction and the longitudinal direction of the liquid crystal polyester film during the heat treatment process.
26. A circuit board substrate, comprising: a liquid crystal polyester film according to any one of claims 1 to 25, which comprises a metal foil; preferably, the metal foil is at least one of copper foil, aluminum foil, gold foil, nickel foil or silver foil; more preferably, the copper foil is a rolled copper foil or an electrolytic copper foil.
27. The circuit board substrate according to claim 26, wherein: the thickness of the metal foil is 9-70 mu m.
28. The circuit board substrate according to claim 26, wherein: the circuit board substrate structure is a laminated structure with two or more layers;
wherein the liquid crystal polyester film layer is adjacent to the metal foil layer.
29. The circuit board substrate according to claim 28, wherein: the circuit board substrate structure is that the structure between the liquid crystal polyester film layer and the metal foil layer is as follows: the liquid crystal polyester film layer and the metal foil layer are of a two-layer structure, or a three-layer structure formed by laminating the metal foil on two sides of the liquid crystal polyester film layer, or a five-layer structure formed by alternately laminating the liquid crystal polyester film layer and the metal foil layer.
30. The circuit board substrate according to claim 26, wherein: the thickness is 10-500 mu m, and the peel strength is more than 0.5N/mm; preferably, the peel strength is greater than 1N/mm.
31. A method for preparing a circuit board substrate according to any one of claims 26 to 30, wherein the method comprises the following steps: the method comprises the following steps:
laminating the metal foil and the liquid crystal polyester film of any one of claims 1 to 25 at a temperature of 250 to 400 ℃ to obtain the circuit board substrate.
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| US20230106477A1 (en) * | 2020-02-21 | 2023-04-06 | Eneos Corporation | Composite, slurry composition, film, and metal-clad laminate |
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